Cleaning method of immersion liquid, immersion liquid cleaning composition, and substrate

ABSTRACT

A cleaning method of an immersion liquid includes supplying an immersion liquid on a surface of a cleaning substrate. The immersion liquid is to be used in a liquid immersion lithography apparatus. The cleaning substrate has a substrate and an organic film laminated on a top face side of the substrate. The immersion liquid is allowed to move on the substrate to remove contaminants from the immersion liquid.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application of theU.S. patent application Ser. No. 13/398,847, filed Feb. 17, 2012. Thecontents of this application are incorporated herein by reference intheir entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a cleaning method of an immersionliquid, an immersion liquid cleaning composition, and a substrate.

2. Discussion of the Background

In manufacture of semiconductor devices, microfabrication by lithographycarried out using a chemically amplified resist composition has beenconventionally carried out. A pattern formation method used in themicrofabrication generally includes: a step of forming a resist film ona substrate; a step of exposure by irradiating the resist film with anactinic ray such as ultraviolet ray through a mask; a step ofdevelopment of the exposed resist film; and a step of etching using theobtained resist pattern as a protective film.

In recent years, enhanced integration of semiconductor devices hasprogressed, and thus further miniaturization of resist patterns inlithography has been demanded. Accordingly, as a method for forming aresist pattern that meets such demands, a liquid immersion lithographyprocess in which a liquid immersion medium (immersion liquid) such ase.g., ultra pure water or a fluorine based inert liquid is filledbetween an exposure lens and the resist film to carry out the exposure(see, Japanese Unexamined Patent Application, Publication No.H10-303114) has been increasingly utilized. The liquid immersionlithography process is advantageous in that the numerical aperture (NA)of the lens can be increased, whereas the focal depth is less likely tobe decreased even if NA is increased, and a high resolving ability canbe attained.

Furthermore, in techniques for improving the liquid immersionlithography process, providing a liquid immersion upper layer film onthe resist film for the purpose of suppressing elution of the resistfilm components into the immersion liquid, and the like, is proposed(see Japanese Unexamined Patent Application, Publication No. 2006-91798,and PCT International Publication No. 2008/47678 and 2009/41270).

However, also when the liquid immersion upper layer film is provided,the immersion liquid may be contaminated with slight amounts of resistfilm components and liquid immersion upper layer film components, orwith dust present in the liquid immersion lithography apparatus during aformation step of a resist pattern carried out using a liquid immersionlithography process. Thus, due to the contaminants immixed in theimmersion liquid, the exposure may be defective, and the resolvingability of the formed resist pattern may be deteriorated; therefore,development of a cleaning method of an immersion liquid, a compositionfor cleaning an immersion liquid, and a substrate which enable animmersion liquid containing such contaminants to be readily andefficiently cleaned to permit reuse has been desired.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, a cleaning method ofan immersion liquid includes supplying an immersion liquid on a surfaceof a cleaning substrate. The immersion liquid is to be used in a liquidimmersion lithography apparatus. The cleaning substrate has a substrateand an organic film laminated on a top face side of the substrate. Theimmersion liquid is allowed to move on the substrate to removecontaminants from the immersion liquid.

According to another aspect of the present invention, an immersionliquid cleaning composition includes a first polymer, a compoundcomponent and a solvent. The compound component consists of at least onecompound selected from the set consisting of a first compound having atleast two groups represented by a following formula (1), a secondcompound having a group represented by a following formula (2) and athird compound having a group represented by a following formula (3).

In the formula (1), R¹ represents a hydrogen atom or a methyl group, andn is an integer of 0 to 10.

In the formula (2), each of R² and R³ each independently represents ahydrogen atom or a group represented by a following formula (ii), and atleast either one of R² and R³ represents a group represented by thefollowing formula (ii).

In the formula (ii), each of R⁴ and R⁵ each independently represents ahydrogen atom, an alkyl group having 1 to 6 carbon atoms or analkoxyalkyl group having 1 to 6 carbon atoms, and, optionally, R⁴ and R⁵bind with each other to form a ring structure together with the carbonatom to which R⁴ and R⁵ each bind, and R⁶ represents a hydrogen atom oran alkyl group having 1 to 6 carbon atoms.

In the formula (3), each of R⁷ and R⁸ independently represents a singlebond, a methylene group, an alkylene group having 2 to 20 carbon atomsor a bivalent cyclic hydrocarbon group having 3 to 20 carbon atoms, R⁹represents an alkyl group having 1 to 20 carbon atoms or a monovalentcyclic hydrocarbon group having 3 to 20 carbon atoms, and m is 0 or 1.

According to further aspect of the present invention, a cleaningsubstrate includes a substrate and an organic film. The organic film islaminated on a top face side of the substrate and made from theimmersion liquid cleaning composition.

DESCRIPTION OF THE EMBODIMENTS

An embodiment of the present invention provides a cleaning method of animmersion liquid for use in a liquid immersion lithography apparatus,the method including

a contaminant removing step of removing contaminants by supplying animmersion liquid on the surface of a substrate having an organic filmlaminated on the top face side thereof, and allowing the immersionliquid to move on the substrate.

By using the cleaning method of an immersion liquid, the immersionliquid containing contaminants immixed in the course of a formationprocess of a resist pattern carried out using a liquid immersionlithography process can be readily and efficiently cleaned to permitreuse.

A composition used in forming the organic film (hereinafter, may be alsoreferred to merely as “composition”) contains

(A) a polymer,

(B) a compound component, and

(C) a solvent,

in which the compound component (B) includes preferably at least onecompound selected from the set consisting of (I) a compound having atleast two groups represented by the following formula (1), (II) acompound having a group represented by the following formula (2), and(III) a compound having a group represented by the following formula(3):

in the formula (1), R¹ represents a hydrogen atom or a methyl group; andn is an integer of 0 to 10;

in the formula (2), R² and R³ each independently represent a hydrogenatom or a group represented by the following formula (ii), and at leasteither one of R² and R³ represents a group represented by the followingformula (ii):

in the formula (ii), R⁴ and R⁵ each independently represent a hydrogenatom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl grouphaving 1 to 6 carbon atoms; and R⁴ and R⁵ may bind with each other toform a ring structure together with a carbon atom to which they eachbind; and R⁶ represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms;

in the formula (3), R⁷ and R⁸ each independently represent a singlebond, a methylene group, an alkylene group having 2 to 20 carbon atomsor a bivalent cyclic hydrocarbon group having 3 to 20 carbon atoms; R⁹represents an alkyl group having 1 to 20 carbon atoms or a monovalentcyclic hydrocarbon group having 3 to 20 carbon atoms; and m is 0 or 1.

Owing to the composition containing the compound component (B) inaddition to the polymer (A) and the solvent (C), the organic film can bestrengthened by a crosslinking reaction of the compound component (B)with the crosslinkable group. As a result, the organic film cancertainly absorb the contaminants, whereby the immersion liquid can beefficiently cleaned.

The compound component (B) more preferably includes at least twocompounds selected from the set consisting of the compound (I), thecompound (II) and the compound (III). The compound component (B)including the aforementioned particular compounds enables the organicfilm to be further strengthened, whereby the immersion liquid can bemore efficiently cleaned.

The polymer (A) preferably has a structural unit (I) represented by thefollowing formula (4):

in the formula (4), R¹⁰ represents a hydrogen atom, a methyl group or atrifluoromethyl group; R¹¹, R¹² and R¹³ each independently represent analkyl group having 1 to 20 carbon atoms or a monovalent alicyclichydrocarbon group having 3 to 20 carbon atoms, and a part or all ofhydrogen atoms of the alkyl group and the alicyclic hydrocarbon groupmay be substituted; and R¹¹ and R¹² may bind with each other to form aring structure together with a carbon atom to which they each bind.

Due to the polymer (A) having the aforementioned particular structuralunit, the immersion liquid can be still more efficiently cleaned.

It is preferred that the composition further contains (D) a polymerhaving at least one fluorine atom (hereinafter, may be also referred toas “(D) polymer”). When the composition further contains the polymer(D), water repellency of the organic film against the immersion liquidcan be improved, and thus the immersion liquid can be smoothly moved onthe organic film.

The polymer (D) preferably has at least one structural unit (II)selected from the set consisting of structural units each represented bythe following formulae (5) and (6):

in the formula (5), R¹⁴ represents a hydrogen atom, a methyl group or atrifluoromethyl group; R¹⁵ represents a single bond, a methylene group,an alkylene group having 2 to 20 carbon atoms, a bivalent alicyclichydrocarbon group having 3 to 20 carbon atoms, a bivalent aromatichydrocarbon group having 6 to 20 carbon atoms, or a combined bivalentgroup of these, and a part or all of hydrogen atoms of the methylenegroup, the alkylene group, the alicyclic hydrocarbon group and thearomatic hydrocarbon group may be substituted; R¹⁶ represents afluorinated methylene group or a fluorinate alkylene group having 2 to20 carbon atoms; and R¹⁷ represents a hydrogen atom or a monovalentorganic group, whereas in the formula (6), R¹⁸ represents a hydrogenatom, a methyl group or a trifluoromethyl group; R¹⁹ represents abivalent linking group; and R²⁰ represents a fluorinated alkyl grouphaving 1 to 20 carbon atoms or a monovalent fluorinated alicyclichydrocarbon group having 3 to 20 carbon atoms.

The polymer (D) having the aforementioned particular structural unit(II) enables the water repellency of the organic film against theimmersion liquid to be still further improved, and the immersion liquidto be cleaned can be more smoothly moved, whereby more efficientcleaning can be executed.

A composition for cleaning an immersion liquid of the embodiment of thepresent invention contains

(A) a polymer,

(B) a compound component, and

(C) a solvent,

in which the compound component (B) includes at least one compoundselected from the set consisting of (I) a compound having at least twogroups represented by the following formula (1), (II) a compound havinga group represented by the following formula (2) and (III) a compoundhaving a group represented by the following formula (3):

in the formula (1), R¹ represents a hydrogen atom or a methyl group; andn is an integer of 0 to 10;

in the formula (2), R² and R³ each independently represent a hydrogenatom or a group represented by the following formula (ii), and at leasteither one of R² and R³ represents a group represented by the followingformula (ii):

in the formula (ii), R⁴ and R⁵ each independently represent a hydrogenatom, an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl grouphaving 1 to 6 carbon atoms, and R⁴ and R⁵ may bind with each other toform a ring structure together with a carbon atom to which they eachbind; and R⁶ represents a hydrogen atom or an alkyl group having 1 to 6carbon atoms;

in the formula (3), R⁷ and R⁸ each independently represent a singlebond, a methylene group, an alkylene group having 2 to 20 carbon atomsor a bivalent cyclic hydrocarbon group having 3 to 20 carbon atoms; R⁹represents an alkyl group having 1 to 20 carbon atoms or a monovalentcyclic hydrocarbon group having 3 to 20 carbon atoms; and m is 0 or 1.

The composition for cleaning an immersion liquid can be used in a methodfor readily and efficiently cleaning the immersion liquid containingcontaminants immixed in the course of a formation process of a resistpattern carried out using a liquid immersion lithography process toenable reuse of the immersion liquid, and can be suitably used forexample, in a cleaning method of the immersion liquid. According to thecomposition for cleaning an immersion liquid, since the compoundcomponent (B) in addition to the polymer (A) and the solvent (C) iscontained, for example, in a method of forming an organic film andcleaning the immersion liquid with the composition for cleaning animmersion liquid, a rigid organic film can be formed owing to acrosslinking reaction between the compound component (B) and thecrosslinkable group.

The compound component (B) more preferably includes at least twocompounds selected from the set consisting of the compound (I), thecompound (II) and the compound (III). The compound component (B)including the aforementioned particular compounds enables the organicfilm to be further strengthened, whereby the immersion liquid can bemore efficiently cleaned.

The polymer (A) preferably has a structural unit (I) represented by thefollowing formula (4):

in the formula (4), R¹⁰ represents a hydrogen atom, a methyl group or atrifluoromethyl group; R¹¹, R¹² and R¹³ each independently represent analkyl group having 1 to 20 carbon atoms or a monovalent alicyclichydrocarbon group having 3 to 20 carbon atoms, and a part or all ofhydrogen atoms of the alkyl group and the alicyclic hydrocarbon groupmay be substituted; and R¹¹ and R¹² may bind with each other to form aring structure together with a carbon atom to which they each bind.

Due to the polymer (A) having the aforementioned particular structuralunit, the immersion liquid can be still more efficiently cleaned.

It is preferred that the composition for cleaning an immersion liquidfurther contains the polymer (D). When the composition for cleaning animmersion liquid further contains the polymer (D), water repellency ofthe organic film against the immersion liquid can be improved, and thusthe immersion liquid can be smoothly moved on the organic film.

The polymer (D) preferably has at least one structural unit (II)selected from the set consisting of structural units each represented bythe following formulae (5) and (6):

in the formula (5), R¹⁴ represents a hydrogen atom, a methyl group or atrifluoromethyl group; R¹⁵ represents a single bond, a methylene group,an alkylene group having 2 to 20 carbon atoms, a bivalent alicyclichydrocarbon group having 3 to 20 carbon atoms, a bivalent aromatichydrocarbon group having 6 to 20 carbon atoms, or a combined bivalentgroup of these, and a part or all of hydrogen atoms of the methylenegroup, the alkylene group, the alicyclic hydrocarbon group and thearomatic hydrocarbon group may be substituted; R¹⁶ represents afluorinated methylene group or a fluorinate alkylene group having 2 to20 carbon atoms; and R¹⁷ represents a hydrogen atom or a monovalentorganic group, whereas in the formula (6), R¹⁸ represents a hydrogenatom, a methyl group or a trifluoromethyl group; R¹⁹ represents abivalent linking group; and R²⁰ represents a fluorinated alkyl grouphaving 1 to 20 carbon atoms or a monovalent fluorinated alicyclichydrocarbon group having 3 to 20 carbon atoms.

The polymer (D) having the aforementioned particular structural unit(II) enables the water repellency of the organic film against theimmersion liquid to be still further improved, and the immersion liquidto be cleaned can be more smoothly moved, whereby more efficientcleaning can be executed.

The substrate of the embodiment of the present invention has a laminatedorganic film formed from the composition for cleaning an immersionliquid.

Since the aforementioned particular composition for cleaning animmersion liquid is used, the substrate has a rigid organic film by wayof a crosslinking reaction of the compound component (B) with acrosslinkable group. As a result, the substrate can be suitably used asa substrate used in, for example, cleaning the immersion liquid.

According to the cleaning method of an immersion liquid, the compositionfor cleaning an immersion liquid, and the substrate of the embodiment ofthe present invention, an immersion liquid containing contaminantsimmixed in the course of a formation process of a resist pattern carriedout using a liquid immersion lithography process can be readily andefficiently cleaned and then reused. As a result, defects resulting fromexposure in the exposure step using a liquid immersion lithographyprocess can be overcome, and thus formation of a finer resist patternthat is superior in resolving ability is enabled. The embodiments willnow be described.

<Cleaning Method of Immersion Liquid>

The cleaning method of an immersion liquid of the embodiment of thepresent invention is a cleaning method of an immersion liquid for use ina liquid immersion lithography apparatus, the method including

a contaminant removing step of removing contaminants by supplying animmersion liquid on the surface of a substrate having an organic filmlaminated on the top face side thereof, and allowing the immersionliquid to move on the substrate. The contaminant removing step isdescribed in detail below.

[Contaminant Removing Step]

In this step, a substrate having an organic film laminated on the topface side thereof is used, and the step is carried out by supplying animmersion liquid on the surface of the substrate, and allowing theimmersion liquid to move on the substrate. Due to this contaminantremoving step included in the cleaning method of an immersion liquid,the immersion liquid containing contaminants immixed in the course of aformation process of a resist pattern carried out using a liquidimmersion lithography process can be readily and efficiently cleaned andreuse thereof is enabled.

The immersion liquid is in general, a liquid having a refractive indexhigher than inert gas such as air and nitrogen, and, for example, purewater, ultra pure water, fluorine-containing inert liquid, or the likemay be included.

The base that serves as a substrate of the organic film may be, forexample, a wafer coated with a metal film of silicon, aluminum or thelike, an insulating film of silicon oxide, silicon nitride, siliconoxynitride, polysiloxane or the like, a low dielectric insulating filmsuch as Black Diamond (manufactured by Applied Materials, Inc., (AMAT)),SiLK™ (manufactured by Dow Chemical Co.,), LKD5109 (manufactured by JSRCorp.), all commercially available products, and the like.

Of these, a wafer coated with a silicon film (hereinafter, may be alsoreferred to as “silicon wafer”) is preferred. In addition, forpreventing back contamination from the substrate into the immersionliquid of the contaminants, the substrate is preferably as clean aspossible.

In the contaminant removing step, the immersion liquid containing thecontaminants is first supplied on the surface of the substrate.

Subsequently, the immersion liquid supplied on the surface of thesubstrate is moved on the substrate.

The process for allowing the immersion liquid to be moved is notparticularly limited, but a liquid contact member is brought intocontact with the top face of the immersion liquid, and the immersionliquid may be allowed to move on the substrate according to the movementof the liquid contact member using the adhesive force between the liquidcontact member and the immersion liquid.

In this step, since the contaminants that reached the surface of thesubstrate by way of diffusive motion are absorbed on the surface of thesubstrate in the immersion liquid, the amount of the contaminantsincluded in the immersion liquid is lowered over time, and concomitantlythe contaminants can be efficiently removed by way of the movement ofthe immersion liquid.

The liquid contact member may be, for example, an exposure lens ofwell-known liquid immersion lithography apparatuses, or the like.

Although the contaminant removing step may be carried out outside theliquid immersion lithography apparatus, it is preferably carried out inthe liquid immersion lithography apparatus. By carrying out this step inthe liquid immersion lithography apparatus, exposure lens can be used asthe liquid contact member, and the immersion liquid can be readily movedby the same method as that for scabbing of the exposure lens in exposingthe resist film by lithography.

Then, after carrying out the contaminant removing step, the cleanedimmersion liquid is usually recovered, and can be reused again in theliquid immersion lithography apparatus.

Although the organic film is not particularly limited as long as it isformed from an organic material, is preferably formed from thecomposition described below. By using the particular composition, acrosslinking reaction with the crosslinkable group enables the organicfilm to be strengthened.

The aforementioned organic film may be a resist film. When the organicfilm is a resist film, the substrate having a resist film formed inlithography can be diverted as a dummy wafer, and thus the cleaningmethod of an immersion liquid can be conveniently performed.

<Composition Used for Formation of Organic Film>

A composition suitably used for forming the organic film contains, forexample, a polymer (A), a compound component (B) and a solvent (C).Also, the composition may contain a polymer (D). Furthermore, thecomposition may contain other component within a range that does notdeteriorate the advantageous effects of the invention. Each component isexplained in detail below.

<(A) Polymer>

The polymer (A) is a main component that constitutes the organic film.Although the polymer (A) is not particularly limited, a polymer havingthe structural unit (I) represented by the above formula (4) ispreferred. The polymer (A) having the aforementioned particularstructural unit serves in enabling the immersion liquid to beefficiently cleaned. It should be noted that the polymer (A) may havetwo or more types of the structural unit (I).

In the above formula (4), R¹⁰ represents a hydrogen atom, a methyl groupor a trifluoromethyl group; R¹¹, R¹² and R¹³ each independentlyrepresent an alkyl group having 1 to 20 carbon atoms or a monovalentalicyclic hydrocarbon group having 3 to 20 carbon atoms, and a part orall of hydrogen atoms of the alkyl group and the alicyclic hydrocarbongroup may be substituted; and R¹¹ and R¹² may bind with each other toform a ring structure together with a carbon atom to which they eachbind.

Examples of the an alkyl group having 1 to 20 carbon atoms representedby R¹¹, R¹² and R¹³ include linear alkyl groups such as a methyl group,an ethyl group, a n-propyl group and a n-butyl group; branched alkylgroups such as an i-propyl group, an i-butyl group, a sec-butyl groupand a t-butyl group, and the like. Of these, a methyl group, and anethyl group are preferred.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20carbon atoms represented by R¹¹, R¹² and R¹³, include monocyclicsaturated hydrocarbon groups such as a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, acyclooctyl group, a cyclodecyl group, a methylcyclohexyl group and anethylcyclohexyl group; monocyclic unsaturated hydrocarbon groups such asa cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, acycloheptenyl group, a cyclooctenyl group, a cyclodecenyl group, acyclopentadienyl group, a cyclohexadienyl group, a cyclooctadienyl groupand cyclodecadiene; polycyclic saturated hydrocarbon groups such as abicyclo[2.2.1]heptyl group, a bicyclo[2.2.2]octyl group, atricyclo[5.2.1.0^(2,6)]decyl group, a tricyclo[3.3.1.1^(3,7)]decylgroup, a tetracyclo[6.2.1.1^(3,6.)0^(2,7)]dodecyl group, a norbornylgroup and an adamantyl group, and the like.

Examples of the group which may substitute for hydrogen atom(s) in thealkyl group and the alicyclic hydrocarbon group represented by R¹¹, R¹²and R¹³ include a hydroxyl group; a carboxyl group; an oxo group;hydroxyalkyl groups having 1 to 4 carbon atoms such as a hydroxymethylgroup, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropylgroup, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group anda 4-hydroxybutyl group; alkoxyl groups having 1 to 4 carbon atoms suchas a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxygroup, a n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxygroup and a t-butoxy group; a cyano group; cyanoalkyl groups having 2 to5 carbon atoms such as a cyanomethyl group, a 2-cyanoethyl group, a3-cyanopropyl group and a 4-cyanobutyl group, and the like. Of these, ahydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group,and a cyanomethyl group are preferred.

<(B) Compound Component>

The compound component (B) reacts with the polymer (A) or (D) a polymerdescribed later by way of an action of an acid or heat, or reactsbetween molecules of the compound component (B) to harden the organicfilm.

This compound component (B) includes at least one compound selected fromthe set consisting of the compound (I) having at least two groupsrepresented by the above formula (1), the compound (II) having the grouprepresented by the above formula (2) and the compound (III) having thegroup represented by the above formula (3), and preferably includes atleast two compounds selected therefrom. When the compound component (B)includes the aforementioned particular compound(s), a crosslinkingreaction between the compound component (B) and a crosslinkable groupenables the organic film to be strengthened. Each compound may beproduced using a well-known technique, and a commercially availableproduct may be used. It is to be noted that each compound may be usedeither only one or two or more types may be used in combination. Eachcompound is described in detail below.

<Compound (I)>

The compound (I) has at least two groups represented by the aboveformula (1). In the above formula (1), R¹ represents a hydrogen atom ora methyl group; and n is an integer of 0 to 10.

The compound (I) is preferably a compound represented by the followingformula (1-1) or (1-2).

In the above formula (1-1), n¹ to n⁴ are each independently an integerof 0 to 10; R^(X1) to R^(X4) each independently represent a hydrogenatom or a group represented by the following formula (1), and at leasttwo of R^(X1) to R^(X4) are the group represented by the followingformula (i), whereas in the above formula (1-2), n⁵ to n¹⁰ are eachindependently an integer of 0 to 10; R^(X5) to R^(X10) eachindependently represent a hydrogen atom or the group represented by thefollowing formula (1), and at least two of R^(X5) to R^(X10) are thegroup represented by the following formula (i):

In the above formula (i), R² has the same meaning as that in the aboveformula (1).

Examples of compound (I) include pentaerythritol triacrylate,pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and thelike.

Examples of commercially available products of the compound (I) includeKAYARAD T-1420 (T), KAYARAD RP-1040, KAYARAD DPHA, KAYARAD DPEA-12,KAYARAD DPHA-2C, KAYARAD D-310 and KAYARAD D-330 (all manufactured byNippon Kayaku Co., Ltd.), NKester ATM-2.4E, NKester ATM-4E, NKesterATM-35E and NKester ATM-4P (all manufactured by Shin Nakamura ChemicalCo., Ltd.), M-309, M-310, M-321, M-350, M-360, M-370, M-313, M-315,M-327, M-306, M-305, M-451, M-450, M-408, M-2035, M-208, M-211B, M-215,M-220, M-225, M-270 and M-240 (all manufactured by To a Gosei Co.,Ltd.), and the like.

<Compound (II)>

The compound (II) has the group represented by the above formula (2). Inthe above formula (2), R² and R³ each independently represent a hydrogenatom or the group represented by the above formula (ii), and at leasteither one of R² and R³ is the group represented by the above formula(ii).

In the above formula (ii), R⁴ and R⁵ each independently represent ahydrogen atom, an alkyl group having 1 to 6 carbon atoms or analkoxyalkyl group having 1 to 6 carbon atoms, and R⁴ and R⁵ may bindwith each other to form a ring structure together with a carbon atom towhich they each bind; and R⁶ represents a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented bythe aforementioned R⁴, R⁵ and R⁶ include linear alkyl groups such as amethyl group, an ethyl group, a n-propyl group and a n-butyl group;branched alkyl groups such as an i-propyl group, an i-butyl group, asec-butyl group and a t-butyl group, and the like.

Examples of the alkoxyalkyl group having 1 to 6 carbon atoms representedby R⁴ and R⁵ include a methoxymethyl group, a methoxyethyl group, anethoxymethyl group, an ethoxyethyl group, a propoxymethyl group, apropoxyethyl group, and the like.

The compound (II) is preferably a compound represented by the followingformula (2-1):

In the above formula (2-1), R² and R³ have the same meaning as those inthe above formula (2); and p is an integer of 1 to 3.

Examples of the compound (II) include nitrogen-containing compounds suchas hexamethoxymethylated melamine, hexabutoxymethylated melamine,tetramethoxymethylated glycoluril and tetrabutoxymethylated glycoluril,and the like.

Furthermore, examples of the commercially available product of thecompound (II) include CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 350, CYMEL232, CYMEL 235, CYMEL 236, CYMEL 238, CYMEL 266, CYMEL 267, CYMEL 285,CYMEL 1123, CYMEL 1123-10, CYMEL 1170, CYMEL 370, CYMEL 771, CYMEL 272,CYMEL 1172, CYMEL 325, CYMEL 327, CYMEL 703, CYMEL 712, CYMEL 254, CYMEL253, CYMEL 212, CYMEL 1128, CYMEL 701, CYMEL 202, CYMEL 207 (allmanufactured by Cytec Industries Inc.), Nikaluck MW-30M, Nikaluck MW-30,Nikaluck MW-22, Nikaluck MW-24X, Nikaluck MS-21, Nikaluck MS-11,Nikaluck MS-001, Nikaluck MX-002, Nikaluck MX-730, Nikaluck MX-750,Nikaluck MX-708, Nikaluck MX-706, Nikaluck MX-042, Nikaluck MX-035,Nikaluck MX-45, Nikaluck MX-410, Nikaluck MX-302, Nikaluck MX-202,Nikaluck SM-651, Nikaluck SM-652, Nikaluck SM-653, Nikaluck SM-551,Nikaluck SM-451, Nikaluck SB-401, Nikaluck SB-355, Nikaluck SB-303,Nikaluck SB-301, Nikaluck SB-255, Nikaluck SB-203, Nikaluck SB-201,Nikaluck BX-4000, Nikaluck BX-37, Nikaluck BX-55H, Nikaluck BL-60 (allmanufactured by Nippon Carbide Industries Co., Inc.), and the like. Ofthese, CYMEL 325, CYMEL 327, CYMEL 703, CYMEL 712, CYMEL 254, CYMEL 253,CYMEL 212, CYMEL 1128, CYMEL 701, CYMEL 202, CYMEL 207, and NikaluckMX-750 are preferred.

<Compound (III)>

The compound (III) has the group represented by the above formula (3).In the above formula (3), R⁷ and R⁸ each independently represent asingle bond, a methylene group, an alkylene group having 2 to 20 carbonatoms or a bivalent cyclic hydrocarbon group having 3 to 20 carbonatoms; R⁹ represents an alkyl group having 1 to 20 carbon atoms or amonovalent cyclic hydrocarbon group having 3 to 20 carbon atoms; and mis 0 or 1.

The alkylene group having 2 to 20 carbon atoms represented by R⁷ and R⁸may be either linear or branched, and examples thereof include amethanediyl group, an ethanediyl group, a propanediyl group, abutanediyl group, a pentanediyl group, a hexanediyl group, and the like.

Exemplary bivalent cyclic hydrocarbon group having 3 to 20 carbon atomsrepresented by R⁷ and R⁸ may include bivalent alicyclic hydrocarbongroups having 3 to 20 carbon atoms, bivalent aromatic hydrocarbon grouphaving 6 to 20 carbon atoms, and the like.

Examples of the bivalent alicyclic hydrocarbon group having 3 to 20carbon atoms include monocyclic saturated hydrocarbon groups such as acyclopropanediyl group, a cyclobutanediyl group and a cyclopentanediylgroup; monocyclic unsaturated hydrocarbon groups such as acyclobutenediyl group, a cyclopentenediyl group and a cyclohexenediylgroup; polycyclic saturated hydrocarbon groups such as abicyclo[2.2.1]heptanediyl group, a bicyclo[2.2.2]octanediyl group and atricyclo[5.2.1.0^(2,6)]decanediyl group; polycyclic unsaturatedhydrocarbon groups such as a bicyclo[2.2.1]heptenediyl group, abicyclo[2.2.2]octenediyl group and a tricyclo[5.2.1.0^(2,6)]decenediylgroup, and the like.

Examples of the bivalent aromatic hydrocarbon group having 6 to 20carbon atoms include a phenylene group, a biphenylene group, aterphenylene group, a benzylene group, a phenyleneethylene group, aphenylenecyclohexylene group, a naphthylene group, and the like.

As the alkyl group having 1 to 20 carbon atoms represented by R⁹, anygroup exemplified in connection with R¹¹, R¹² and R¹⁹ may be employed.

Examples of the monovalent cyclic hydrocarbon group having 3 to 20carbon atoms represented by R⁹ include a phenyl group, a biphenyl group,a terphenyl group, a benzyl group, a naphthyl group, and the like.

The compound (III) is preferably a compound represented by the followingformula (3-1):

In the above formula (3-1), R⁸, R⁹ and m have the same meaning as thosein the above formula (3); and q is an integer of 1 to 3.

Examples of the compound (III) include 1,6-hexanediol diglycidyl ether,dipentaerythritolhexakis(3-ethyl-3-oxetanylmethyl)ether, and the like.

Furthermore, examples of the commercially available product of thecompound (III) include ARONE OXETANE OXT-101, ARONE OXETANE OXT-121 andARONE OXETANE OXT-221 (all manufactured by To a Gosei Co., Ltd.), OXMA,OXTP, OXBP and OXIPA (all manufactured by Ube Industries, Ltd.) and thelike. Of these, OXIPA is preferred.

The content of the compound component (B) is preferably no less than 1part by mass and no greater than 100 parts by mass, and more preferablyno less than 1 part by mass and no greater than 50 parts by mass withrespect to 100 parts by mass of the polymer (A). When the content isless than 1 part by mass, the crosslinking reaction of the organic filmmay be insufficient, and thus the immersion liquid may be contaminatedresulting from detachment of the film. To the contrary, when the contentexceeds 100 parts by mass, unreacted compound component (B) may beincluded in the immersion liquid, whereby the immersion liquid may becontaminated.

<(C) Solvent>

The solvent (C) which may be suitably used can uniformly dissolve ordisperse each component, and does not react with each component. Itshould be noted that the solvent (C) used may be of one type, or acombination of two or more types.

Examples of the solvent (C) include ketones, propylene glycol monoalkylether acetates, 2-hydroxypropionic acid alkyls, 3-alkoxypropionic acidalkyls, γ-butyrolactone, and the like.

Examples of the ketones include methyl ethyl ketone, methyl isobutylketone, 2-heptanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, andthe like.

Examples of the propylene glycol monoalkyl ether acetates includepropylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate, propylene glycol monopropyl ether acetate, propyleneglycol monobutyl ether acetate, and the like.

Examples of the 2-hydroxypropionic acid alkyls include methyl2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl2-hydroxypropionate, and the like.

Examples of the 3-alkoxypropionic acid alkyls include methyl3-methoxypropionate, ethyl 3-methoxypropionate, methyl3-ethoxypropionate, ethyl 3-ethoxypropionate, and the like.

Among these, propylene glycol monomethyl ether acetate, 2-heptanone, andcyclohexanone are preferred.

The content of the solvent (C) should be adjusted such that theconcentration of the solid content included in the composition becomesusually no less than 2% by mass and no greater than 70% by mass,suitably no less than 4% by mass and no greater than 25% by mass, andmore suitably no less than 4% by mass and no greater than 10% by mass.When a solvent other than propylene glycol monomethyl ether acetate,2-heptanone and cyclohexanone is used in combination with any of thesesolvents, the content of the solvent other than propylene glycolmonomethyl ether acetate, 2-heptanone and cyclohexanone is usually nogreater than 50% by mass, suitably no greater than 30% by mass, and moresuitably no greater than 25% by mass with respect to the total solvent.

<(D) Polymer>

The polymer (D) is a polymer having a fluorine atom. The composition mayor may not contain the polymer (D). When the composition contains thepolymer (D), water repellency of the organic film against the immersionliquid can be improved, and thus the immersion liquid can be smoothlymoved on the substrate.

Although the polymer (D) is not particularly limited as long as it has afluorine atom, and it preferably has at least one structural unit (II)selected from the set consisting of structural units each represented bythe above formula (5) and (6). When the polymer (D) has theaforementioned particular structural unit (II), the water repellency ofthe organic film against the immersion liquid can be further improved,and thus the immersion liquid can be even more smoothly moved on thesubstrate. It is to be noted that the polymer (D) may include two ormore types of the structural unit (II).

In the above formula (5), R¹⁴ represents a hydrogen atom, a methyl groupor a trifluoromethyl group; R¹⁵ represents a single bond, a methylenegroup, an alkylene group having 2 to 20 carbon atoms, a bivalentalicyclic hydrocarbon group having 3 to 20 carbon atoms, a bivalentaromatic hydrocarbon group having 6 to 20 carbon atoms, or a combinedbivalent group of these, and a part or all of hydrogen atoms of themethylene group, the alkylene group, the alicyclic hydrocarbon group andthe aromatic hydrocarbon group may be substituted with a substituent;R¹⁶ represents a fluorinated methylene group or a fluorinate alkylenegroup having 2 to 20 carbon atoms; and R¹⁷ represents a hydrogen atom ora monovalent organic group.

In the above formula (6), R¹⁸ represents a hydrogen atom, a methyl groupor a trifluoromethyl group; R¹⁹ represents a bivalent linking group; andR²⁰ represents a fluorinated alkyl group having 1 to 20 carbon atoms ora monovalent fluorinated alicyclic hydrocarbon group having 3 to 20carbon atoms.

The alkylene group having 2 to 20 carbon atoms represented by R¹⁵ may beeither linear or branched, and examples thereof include a methanediylgroup, an ethanediyl group, a propanediyl group, a butanediyl group, apentanediyl group, a hexanediyl group, and the like.

Examples of the bivalent alicyclic hydrocarbon group having 3 to 20carbon atoms represented by R¹⁵ include monocyclic saturated hydrocarbongroups such as a cyclopropanediyl group, a cyclobutanediyl group and acyclopentanediyl group; monocyclic unsaturated hydrocarbon groups suchas a cyclobutenediyl group, a cyclopentenediyl group and acyclohexenediyl group; polycyclic saturated hydrocarbon groups such as abicyclo[2.2.1]heptanediyl group and a bicyclo[2.2.2]octanediyl group;polycyclic unsaturated hydrocarbon groups such as abicyclo[2.2.1]heptenediyl group and a bicyclo[2.2.2]octenediyl group,and the like.

Examples of the bivalent aromatic hydrocarbon group having 6 to 20carbon atoms represented by R¹⁵ include a phenylene group, a biphenylenegroup, a terphenylene group, a benzylene group, a phenyleneethylenegroup, a phenylenecyclohexylene group, a naphthylene group, and thelike.

Examples of the substituent for hydrogen atom(s) of the methylene group,the alkylene group, the alicyclic hydrocarbon group and the aromatichydrocarbon group represented by R¹⁵ include a hydroxyl group, a cyanogroup, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxylgroup, an oxygen atom, and the like.

Examples of R¹⁵ include groups each represented by the followingformulae, and the like.

In the above formulae, “*” denotes a binding site.

The bivalent group represented by R¹⁵ is preferably a methylene group,an ethylene group, a 1-methylethylene group, a 2-methylethylene group, abivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or agroup substituted with the aforementioned substituent.

The fluorinated alkylene group having 2 to 20 carbon atoms representedby R¹⁶ is obtained by substituting a part or all of hydrogen atoms ofthe alkylene group having 2 to 20 carbon atoms with a fluorine atom.

The alkylene group having 2 to 20 carbon atoms may be either linear orbranched, and examples thereof include an ethanediyl group, apropanediyl group, a butanediyl group, a pentanediyl group, a hexanediylgroup, and the like.

Examples of the fluorinated methylene group or the fluorinated alkylenegroup having 2 to 20 carbon atoms represented by R¹⁶ include groups eachrepresented by the following formulae, and the like.

In the above formulae, “*” denotes a binding site.

Examples of the monovalent organic group represented by R¹⁷ includeacid-dissociable group, monovalent hydrocarbon groups having 1 to 20carbon atoms (excluding acid-dissociable groups), and the like. It is tobe noted that the acid-dissociable group as referred to means a groupthat substitutes for hydrogen atom(s) of a polar functional group suchas, e.g., a hydroxyl group, a carboxyl group and the like, and isdissociated in the presence of an acid.

Examples of the acid-dissociable group include groups represented by thefollowing formula, and the like.

In the above formula, R^(b1), R^(b2) and R^(b3) each independentlyrepresent an alkyl group having 1 to 20 carbon atoms or a monovalentalicyclic hydrocarbon group having 3 to 20 carbon atoms, and a part orall of hydrogen atoms of the alkyl group and the alicyclic hydrocarbongroup may be substituted; R^(b1) and R^(b2) may bind to form a ringstructure together with a carbon atom to which they each bind.

As the alkyl group having 1 to 20 carbon atoms and the monovalentalicyclic hydrocarbon group having 3 to 20 carbon atoms represented byR^(b1), R^(b2) and R^(b3), any group exemplified in connection with R¹¹,R¹² and R¹³ may be employed.

Examples of the group which may substitute for hydrogen atom(s) in thealkyl group and the alicyclic hydrocarbon group include linear, branchedor cyclic alkyl groups having 1 to 4 carbon atoms such as a methylgroup, an ethyl group, a n-propyl group, an i-propyl group, a n-butylgroup, a 2-methylpropyl group, a 1-methylpropyl group and a t-butylgroup, and the like.

The monomer capable of providing the structural unit represented by theabove formula (5) is preferably a monomer represented by the followingformulae.

Examples of the bivalent linking group represented by R¹⁹ include asingle bond, an oxygen atom, a sulfur atom, a carbonyloxy group, anoxycarbonyl group, an amide group, a sulfonylamide group, a urethanegroup, and the like.

The fluorinated alkyl group having 1 to 20 carbon atoms represented byR²⁰ is obtained by substituting a part or all of hydrogen atoms of thealkyl group having 1 to 20 carbon atoms with a fluorine atom.

As the alkyl group having 1 to 20 carbon atoms, any group exemplified inconnection with R¹¹, R¹² and R¹³ may be employed.

The monovalent fluorinated alicyclic hydrocarbon group having 3 to 20carbon atoms represented by R²⁰ is obtained by substituting a part orall of hydrogen atoms of the monovalent alicyclic hydrocarbon grouphaving 3 to 20 carbon atoms with a fluorine atom.

As the monovalent alicyclic hydrocarbon group having 3 to 20 carbonatoms, any group exemplified in connection with R¹¹, R¹² and R¹³ may beemployed.

Examples of the monomer capable of providing the structural unitrepresented by the above formula (6) include trifluoromethyl(meth)acrylic ester, 2,2,2-trifluoroethyl (meth)acrylic ester,perfluoroethyl (meth)acrylic ester, perfluoron-propyl (meth)acrylicester, perfluoroi-propyl (meth)acrylic ester, perfluoron-butyl(meth)acrylic ester, perfluoroi-butyl (meth)acrylic ester,perfluoro-t-butyl (meth)acrylic ester, 2-(1,1,1,3,3,3-hexafluoropropyl)(meth)acrylic ester, 1-(2,2,3,3,4,4,5,5-octafluoropentyl) (meth)acrylicester, perfluorocyclohexylmethyl (meth)acrylic ester,1-(2,2,3,3,3-pentafluoropropyl) (meth)acrylic ester,1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)(meth)acrylic ester,1-(5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluorohexyl) (meth)acrylicester, and the like.

The content of the structural unit (II) with respect to the totalstructural units in the polymer (D) is usually no less than 5% by mole,more preferably no less than 10% by mole, and still more preferably noless than 15% by mole. When the content of the structural unit (II)falls within the aforementioned particular range, the water repellencyof the organic film can be efficiently improved.

The content of the polymer (D) with respect to 100 parts by mass of thepolymer (A) is preferably no less than 0.1 parts by mass and no greaterthan 20 parts by mass, and more preferably no less than 1 part by massand no greater than 10 parts by mass. When the content of the polymer(D) falls within the aforementioned particular range, water repellencyof the organic film can be efficiently improved, and thus the immersionliquid can be smoothly moved on the organic film.

<Other Components>

The composition may contain other components within a range that doesnot deteriorate the advantageous effects of the invention. The othercomponent may include, for example, when the organic film is a resistfilm, an acid generator, an acid diffusion controlling agent, asurfactant, a sensitizer, an alicyclic additive, and the like. Eachcomponent is described in detail below.

<Acid Generator>

The acid generator is a component that generates an acid throughdegradation by exposure or heat. The acid generator may include, forexample, an ionic compound, and the like. The acid generator used may beof one type, or a combination of two or more types.

Examples of the cation of the ionic compound include triphenylsulfoniumcation, tri-1-naphthylsulfonium cation, tri-tert-butylphenylsulfoniumcation, 4-fluorophenyl-diphenylsulfonium cation,di-4-fluorophenyl-phenylsulfonium cation, tri-4-fluorophenylsulfoniumcation, 4-cyclohexylphenyl-diphenylsulfonium cation,4-methanesulfonylphenyl-diphenylsulfonium cation,4-cyclohexanesulfonyl-diphenylsulfonium cation,1-naphthyldimethylsulfonium cation, 1-naphthyldiethylsulfonium cation,1-(4-hydroxynaphthyl)dimethylsulfonium cation,1-(4-methylnaphthyl)dimethylsulfonium cation,1-(4-methylnaphthyl)diethylsulfonium cation,1-(4-cyanonaphthyl)dimethylsulfonium cation,1-(4-cyanonaphthyl)diethylsulfonium cation,1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium cation,1-(4-methoxynaphthyl)tetrahydrothiophenium cation,1-(4-ethoxynaphthyl)tetrahydrothiophenium cation,1-(4-n-propoxynaphthyl)tetrahydrothiophenium cation,1-(4-n-butoxynaphthyl)tetrahydrothiophenium cation,2-(7-methoxynaphthyl)tetrahydrothiophenium cation,2-(7-ethoxynaphthyl)tetrahydrothiophenium cation,2-(7-n-propoxynaphthyl)tetrahydrothiophenium cation,2-(7-n-butoxynaphthyl)tetrahydrothiophenium cation, and the like.

Examples of the anion of the ionic compound includetrifluoromethanesulfonate anion, nonafluoro-n-butanesulfonate anion,perfluoro-n-octanesulfonate anion,2-bicyclo[2.2.1]heptane-2-yl-1,1,2,2-tetrafluoroethanesulfonate anion,2-bicyclo[2.2.1]heptane-2-yl-1,1-difluoroethanesulfonate anion, and thelike.

The content of the acid generator when added is preferably 0.1 to 20parts by mass, and more preferably 0.5 to 10 parts by mass with respectto 100 parts by mass of the total polymer. When the content of the acidgenerator falls within the aforementioned particular range, thecrosslinking reaction can be efficiently promoted.

<Acid Diffusion Controlling Agent>

The acid diffusion controlling agent is a component that suppressesdiffusion of an acid generated from the acid generator due to exposurein the composition. When the composition contains the acid diffusioncontrolling agent, storage stability of the composition can be improved.The acid diffusion controlling agent used may be of one type, or acombination of two or more types.

Examples of the acid diffusion controlling agent include(R)-(+)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol,N-t-butoxycarbonylpyrrolidine, triphenylsulfonium salicylate, and thelike.

The content of the acid diffusion controlling agent when added isusually no less than 0.001 parts by mass and no greater than 15 parts bymass, preferably no less than 0.001 parts by mass and no greater than 10parts by mass, and more preferably no less than 0.001 parts by mass andno greater than 5 parts by mass with respect to 100 parts by mass of thetotal polymer. When the content of the acid diffusion controlling agentfalls within the aforementioned particular range, the storage stabilityof the composition can be efficiently improved.

<Surfactant>

The surfactant is a component that improves the coating property. Whenthe composition contains the surfactant, nonuniform coating of thecomposition is reduced, and thus lamination of a uniform organic film isenabled. The surfactant used may be of one type, or a combination of twoor more types.

Examples of the surfactant include nonionic surfactants such aspolyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether,polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate andpolyethylene glycol distearate, and the like. Also, examples of thecommercially available product of the surfactant include KP341(manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75 andPolyflow No. 95 (all manufactured by Kyoeisha Chemical Co., Ltd.), EFTOPEF301, EFTOP EF303 and EFTOP EF352 (all manufactured by Tochem Products,Co., Ltd.,), Megaface® F171 and Megaface® F173 (all manufactured byDainippon Ink And Chemicals, Incorporated), Florade FC430 and FloradeFC431 (all manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, SurflonS-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, and SurflonSC-104, Surflon SC-105 and Surflon SC-106 (all manufactured by AsahiGlass Co., Ltd.), and the like.

The content of the surfactant when added is usually no greater than 2parts by mass with respect to 100 parts by mass of the total polymer.When the content of the surfactant falls within the aforementionedparticular range, the coating property can be efficiently improved.

<Sensitizer>

The sensitizer is a component that accelerates production of an acidfrom the acid generator by way of radiation. The sensitizer used may beof one type, or a combination of two or more types.

Examples of the sensitizer include carbazoles, acetophenones,benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal,pyrenes, anthracenes, phenothiazines, and the like.

The content of the sensitizer when added is usually no greater than 50parts by mass with respect to 100 parts by mass of the total polymer.

<Alicyclic Additive>

The alicyclic additive is a component that improves the adhesiveness.When the composition contains the alicyclic additive, a substrate havinga highly adhesive organic film laminated thereon can be obtained. Thealicyclic additive used may be of one type, or a combination of two ormore types.

Examples of the alicyclic additive include adamantane derivatives suchas t-butyl 1-adamantane carboxylate, and the like.

The content of the alicyclic additive when added is usually no greaterthan 50 parts by mass, and more preferably no greater than 30 parts bymass with respect to 100 parts by mass of the total polymer.

<Synthesis Method of Each Polymer>

In the method of synthesizing the polymer (A) and the polymer (D), forexample, a monomer corresponding to each predetermined structural unitis polymerized using a polymerization initiator, in an appropriatepolymerization solvent, thereby enabling the synthesis.

Examples of the polymerization initiator include2,2′-azobisisobutyronitrile,2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis(2-cyclopropylpropionitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(2-methylpropionitrile), dimethyl 2,2-azobisisobutyrate, andthe like. The polymerization initiator used may be of one type, or acombination of two or more types.

Examples of the polymerization solvent include alkanes such asn-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane;cycloalkanes such as cyclohexane, cycloheptane, cyclooctane,decaphosphorus and norbornane; aromatic hydrocarbons such as benzene,toluene, xylene, ethylbenzene and cumene; chlorobutanes; bromohexanes;dichloroethanes; halogenated hydrocarbons such as hexamethylenedibromideand chlorobenzene; saturated carboxylate esters such as ethyl acetate,n-butyl acetate, i-butyl acetate and methyl propionate; ethers such astetrahydrofuran, dimethoxyethane and diethoxyethane; alcohols such asmethanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol,isobutyl alcohol, 1-pentanol, 3-pentanol, 4-methyl-2-pentanol,o-chlorophenol and 2-(1-methylpropyl)phenol; ketones such as acetone,2-butanone, 3-methyl-2-butanone, 4-methyl-2-pentanone, 2-heptanone,cyclopentanone, cyclohexanone and methylcyclohexanone, and the like. Thepolymerization solvent used may be of one type, or a combination of twoor more types.

Each polymer obtained by the polymerization reaction is recoveredpreferably by a reprecipitation technique. More specifically, aftercompleting the polymerization reaction, the polymerization liquid ischarged in a reprecipitation solvent, and the intended polymer isrecovered in the form of powder. As the reprecipitation solvent, analcohol, an alkane or the like may be used either alone or incombination of two or more thereof. Apart from the reprecipitationmethod, liquid-separation operation as well as column operation,ultrafiltration operation or the like may be employed to remove lowmolecular components, whereby each polymer may be recovered.

The reaction temperature and the reaction time of these synthesismethods may be determined ad libitum depending on the monomer thatprovides each structural unit, the type of the polymerization initiatoremployed, and the like.

The weight average molecular weight (Mw) of each polymer in terms ofpolystyrene on gel permeation chromatography (GPC) is usually 1,000 to500,000, preferably 1,000 to 100,000, and more preferably 1,000 to50,000. When the Mw is less than 1,000, the heat resistance of thecomposition may deteriorate. Whereas, the Mw being greater than 500,000may lead to deterioration of the adhesiveness of the organic filmlaminated. In addition, Mw/Mn, a ratio of Mw with respect to the numberaverage molecular weight (Mn) in terms of polystyrene on GPC ispreferably 1 to 5, and more preferably 1 to 3.

The Mw and Mn as referred to herein are measured by GPC using GPCcolumns manufactured by Tosoh Corporation (G2000HXL×2, G3000HXL×1, andG4000HXL×1) under the analytical conditions including a flow rate of 1.0mL/min, an elution solvent of tetrahydrofuran and a column temperatureof 40° C., with mono-dispersed polystyrene as a standard.

The proportion of the low molecular weight components having a molecularweight of less than 1,000 remaining in each polymer is preferably nogreater than 0.1% by mass in terms of the solid content with respect tothe entirety of each polymer. The proportion of the low molecular weightcomponents herein is measured using a column manufactured by GLSciences, Inc., (Intersil ODS-25 μm column, 4.6 mmφ×250 mm) under theanalytical conditions including a flow rate of 1.0 mL/min and an elutionsolvent of acrylonitrile/0.1% aqueous phosphoric acid solution, withhigh performance liquid chromatography (HPLC).

<Method of Preparation of Composition>

The composition may be prepared by mixing specified amounts of thepolymer (A), the compound component (B), the polymer (D) and the othercomponents while adjusting the amount of the solvent (C) used such thatthe concentration of the solid content becomes no less than 2% by massand no greater than 70% by mass.

<Method for Producing Substrate Having Organic Film Laminated on the TopFace Side Thereof>

In a typically exemplified method for producing a substrate having anorganic film laminated on the top face side thereof, the aforementionedcomposition is applied on, for example, a silicon wafer, which issubjected to a heat treatment, thereby laminating an organic film. Withrespect application of the composition, for example, a spin coatingmethod, a roll coating method, a dip coating method, or the like may beemployed. In addition, the heat treatment may be carried out once, ortwice or more times stepwise. The heating temperature is usually 50° C.to 250° C., and preferably 100° C. to 200° C. The heating time isusually 30 sec to 300 sec, and preferably 60 sec to 180 sec. The filmthickness of the organic film is preferably 30 nm to 500 nm.

<Composition for Cleaning Immersion Liquid>

A composition for cleaning an immersion liquid of the embodiment of thepresent invention contains the polymer (A), the compound component (B)and the solvent (C), in which the compound component (B) includes atleast one compound selected from the set consisting of the compound (I)having at least two groups represented by the above formula (1), thecompound (II) having the group represented by the above formula (2) andthe compound (III) having the group represented by the above formula(3).

The composition for cleaning an immersion liquid may be used in a methodfor cleaning readily and efficiently an immersion liquid containingcontaminants immixed in the course of a formation process of a resistpattern carried out using a liquid immersion lithography process topermit reuse of the same, and the composition can be suitably used in,for example, the cleaning method of an immersion liquid of the presentinvention. According to the composition for cleaning an immersion liquidof the embodiment of the present invention, since in addition to thepolymer (A), the solvent (C), the compound component (B) is contained, arigid organic film can be formed by way of a crosslinking reactionbetween the compound component (B) and a crosslinkable group in, forexample, a method of forming an organic film and cleaning the immersionliquid with the composition for cleaning the immersion liquid.

It is to be noted that the composition for cleaning an immersion liquidof the embodiment of the present invention is the same as thecomposition used in forming the above mentioned organic film; therefore,explanation in this section is omitted sine it is detailed in the aboverelevant section and the like.

<Substrate>

The substrate of the embodiment of the present invention has a laminatedorganic film formed from the composition for cleaning an immersionliquid. This substrate has a rigid organic film due to a crosslinkingreaction between the compound component (B) and a crosslinkable groupwhen the aforementioned particular composition for cleaning an immersionliquid is used. As a result, the substrate can be suitably used as, forexample, a substrate used in the cleaning method of the immersionliquid.

It is to be noted that the substrate of the embodiment of the presentinvention is the same as the substrate explained in connection with theaforementioned cleaning method of an immersion liquid; therefore,explanation in this section is omitted sine it is detailed in the aboverelevant section and the like.

EXAMPLES

Hereinafter, the present invention is explained more specifically by wayof Examples, but the present invention is not limited to these Examples.

<Synthesis of Each Polymer>

Using monomers represented by the following formulae (M-1) to (M-11),respectively, each polymer was synthesized.

<Synthesis of Polymer (A)>

Synthesis Example 1 Synthesis of (A-1)

Into a flask were charged 50.4 g (50% by mole) of (M-1), 37.2 g (35% bymole) of (M-2) and 12.4 g (15% by mole) of (M-3) as monomers, 4.03 g of2,2′-azobisisobutyronitrile as a polymerization initiator, and 200 g of2-butanone as a polymerization solvent, and a polymerization reactionwas allowed by stirring under nitrogen at 80° C. for 6 hours. Aftercompleting the polymerization reaction, the polymerize solution wascooled with water to 30° C. or below, and then the mixture was chargedinto 200 g of methanol. The powder thus deposited was filtered off. Thepowder obtained by filtration was washed twice with 400 g of methanol,and again filtered off, followed by drying at 50° C. for 17 hours toobtain a polymer (A-1) (yield: 75 g; yield percentage: 75%). Thispolymer had a Mw of 6,900, and the Mw/Mn was 1.4. As a result of a¹³C-NMR analysis, the contents of structural units derived from (M-1),(M-2) and (M-3) were 50.9% by mole, 34.6% by mole and 14.5% by mole,respectively. Note that herein the ¹³C-NMR analysis carried out fordetermining the content (% by mole) of each structural unit in thepolymer used a nuclear magnetic resonance apparatus (JNM-EX270,manufactured by JEOL, Ltd.).

Synthesis Example 2 Synthesis of (A-2)

A polymer (A-2) was obtained (yield: 80 g; yield percentage: 80%) by asimilar operation to Synthesis Example 1 except that 40.17 g (40% bymole) of (M-1), 37.06 g (45% by mole) of (M-4) and 22.77 g (15% by mole)of (M-5) were charged as monomers. This polymer had a Mw of 6,100, andthe Mw/Mn was 1.4. As a result of the ¹³C-NMR analysis, the contents ofstructural units derived from (M-1), (M-4) and (M-5) were 40.0% by mole,45.0% by mole and 15.0% by mole, respectively.

Synthesis Example 3 Synthesis of (A-3)

A polymer (A-3) was obtained (yield: 78 g; yield percentage: 78%) by asimilar operation to Synthesis Example 1 except that 41.49 g (40% bymole) of (M-1), 21.87 g (20% by mole) of (M-2), 23.55 g (30% by mole) of(M-4) and 13.08 g (10% by mole) of (M-6) were charged as monomers. Thispolymer had a Mw of 9,000, and the Mw/Mn was 1.3. As a result of the¹³C-NMR analysis, the contents of structural units derived from (M-1),(M-2), (M-4) and (M-6) were 42.0% by mole, 20.5% by mole, 28.0% by moleand 9.5% by mole, respectively.

Synthesis Example 4 Synthesis of (A-4)

A polymer (A-4) was obtained (yield: 80 g; yield percentage: 80%) by asimilar operation to Synthesis Example 1 except that 48.39 g (50% bymole) of (M-8) and 51.61 g (50% by mole) of (M-10) were charged asmonomers. This polymer had a Mw of 10,000, and the Mw/Mn was 1.4. As aresult of the ¹³C-NMR analysis, the contents of structural units derivedfrom (M-8) and (M-10) were 51.0% by mole and 49.0% by mole,respectively.

Synthesis Example 5 Synthesis of (A-5)

A polymer (A-5) was obtained (yield: 85 g; yield percentage: 85%) by asimilar operation to Synthesis Example 1 except that 45.80 g (50% bymole) of (M-8) and 54.20 g (50% by mole) of (M-9) were charged asmonomers. This polymer had a Mw of 12,000, and the Mw/Mn was 1.4. As aresult of the ¹³C-NMR analysis, the contents of structural units derivedfrom (M-8) and (M-9) were 51.5% by mole and 48.5% by mole, respectively.

<Synthesis of Polymer (D)>

Synthesis Example 6 Synthesis of (D-1)

A polymer (D-1) was obtained (yield: 81 g; yield percentage: 81%) by asimilar operation to Synthesis Example 1 except that 68.01 g (70% bymole) of (M-3) and 31.99 g (30% by mole) of (M-7) were charged asmonomers. This polymer had a Mw of 7,500, and the Mw/Mn was 1.3. As aresult of the ¹³C-NMR analysis, the contents of structural units derivedfrom (M-3) and (M-7) were 70.0% by mole and 30.0% by mole, respectively.

Synthesis Example 7 Synthesis of (D-2)

A polymer (D-2) was obtained (yield: 70 g; yield percentage: 70%) by asimilar operation to Synthesis Example 1 except that 81.39 g (85% bymole) of (M-3) and 18.61 g (15% by mole) of (M-11) were charged asmonomers. This polymer had a Mw of 7,500, and the Mw/Mn was 1.4. As aresult of the ¹³C-NMR analysis, the contents of structural units derivedfrom (M-3) and (M-11) were 84.2% by mole and 15.8% by mole,respectively.

<Preparation of Composition>

Using each polymer thus synthesized, and the compound component (B), thesolvent (C), the acid generator (E) and the acid diffusion controllingagent (F) described below, each composition was prepared according tothe type and the amount used of each component shown in Tables 1-1 and1-2. In Tables 1-1 and 1-2, the designation “-” in the column indicatesthat the component was not contained.

(B) Compound Component

B-1: trade name “Nikaluck MX-750” (manufactured by Nippon CarbideIndustries Co., Inc.)

B-2: pentaerythritol tetraacrylate

B-3: trade name “OXIPA” (manufactured by Ube Industries, Ltd.)

B-4: pentaerythritol triacrylate

(C) Solvent

C-1: propylene glycol monomethyl ether acetate

C-2: cyclohexanone

(E) Acid Generator

E-1: 4-cyclohexylphenyl-diphenylsulfoniumnonafluoro-n-butanesulfonate

E-2: triphenylsulfoniumnonafluoro-n-butanesulfonate

E-3: triphenylsulfonium2-(bicyclo[2.2.1]heptane-2-yl)-1,1-difluoroethanesulfonate

(F) Acid Diffusion Controlling Agent

F-1: (R)-(+)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanolN-t-butoxycarbonylpyrrolidine

F-2: triphenylsulfonium salicylate

TABLE 1-1 (B) Compound (E) Acid (F) Acid diffusion (A) Polymer component(C) Solvent (D) Polymer generator controlling agent Amount Amount AmountAmount Amount Amount used used used used used used (parts (parts (parts(parts (parts by (parts by Composition Type by mass) Type by mass) Typeby mass) Type by mass) Type mass) Type mass) Composition (1) A-1 100 B-120 C-1 1,015 D-1 3 E-1 6 F-1 0.5 C-2 435 E-2 1 Composition (2) A-2 100B-1 10 C-1 1,015 D-1 3 E-2 7 F-1 0.5 B-4 30 C-2 435 Composition (3) A-3100 B-1 10 C-1 1,015 D-1 3 — — — — B-3 30 C-2 435 Composition (4) A-1100 B-1 10 C-1 1,015 D-1 3 E-1 6 F-1 0.5 B-2 30 C-2 435 E-2 1Composition (5) A-3 100 B-1 10 C-1 1,015 D-1 3 — — — — C-2 435Composition (6) A-2 100 B-4 30 C-1 1,015 — — E-1 6 F-1 0.5 C-2 435 E-3 1

TABLE 1-2 (B) Compound (E) Acid (F) Acid diffusion (A) Polymer component(C) Solvent (D) Polymer generator controlling agent Amount Amount AmountAmount Amount Amount used used used used used used (parts (parts (parts(parts (parts by (parts by Composition Type by mass) Type by mass) Typeby mass) Type by mass) Type mass) Type mass) Composition (7) A-3 100 B-110 C-1 1,015 D-1 3 E-2 7 F-1 0.5 B-4 30 C-2 435 Composition (8) A-5 100B-1 10 C-1 1,015 D-1 3 — — — — B-3 30 C-2 435 Composition (9) A-4 100B-1 10 C-1 1,015 D-1 3 E-1 6 F-1 0.5 B-2 30 C-2 435 E-2 1 Composition(10) A-5 100 B-1 10 C-1 1,015 D-1 3 — — — — C-2 435 Composition (11) A-4100 B-1 10 C-1 1,015 D-1 3 — — — — C-2 435 Composition (12) A-3 100 B-110 C-1 1,015 D-2 3 — — — — C-2 435 Composition (13) A-4 100 B-1 10 C-11,015 D-2 3 E-1 6 F-1 0.5 C-2 435 E-3 1

<Production of Substrate Having Laminated Organic Film>

Each composition was spin coated on a silicon wafer, which was thensubjected to a heat treatment under the “First heat treatment”conditions shown in Table 2, followed by a further heat treatment underthe “Second heat treatment” conditions show in the same Table to producea substrate provided with an organic film having a film thickness of 55nm laminated thereon. The film thickness of the organic film wasmeasured using a film thickness measurement system (Lamda Ace VM-90(manufactured by Dainippon Screen Mfg. Co., Ltd.).

<Evaluation>

Contaminant removing capability, water repellency and peel resistancewere determined, and the results of each determination are shown inTable 2. In Table 2, the designation “-” in the column indicates thatthe component was not contained, or the heat treatment was not carriedout. Also, the substrate of Comparative Example not having an organicfilm laminated thereon was the same silicon wafer used as the substrateon which an organic film was laminated.

[Contaminant Removing Capability]

After determining the contaminants on the surface of the substrate, aliquid immersion lithography apparatus (NSR S610C, manufactured byNIKON) was used to bring the immersion liquid into contact with exposurelens, and the immersion liquid (ultra pure water) was moved on thesubstrate as in actual exposure. Then, the immersion liquid was removedand the contaminants on the surface of the substrate were determinedagain to derive the contaminant removing capability from the results ofdetermination. When the contaminants on the surface of the substrateincreased after removing the immersion liquid as compared with thecontaminants before supplying the same, the contaminant removingcapability was evaluated to be favorable “A” presuming that removal thecontaminants which had been included in the immersion liquid wasindicated, whereas the contaminant removing capability was evaluated tobe inferior “B” when the contaminants on the surface of the substratedecreased after the removal of the immersion liquid, presuming that anincrease in the contaminants included in the immersion liquid wasindicated. It is to be noted that the contaminants on the surface of thesubstrate were determined using a Brightfield Patterned Wafer Inspector(KLA2810, manufactured by KLA-Tencor Corporation).

[Water Repellency]

The substrate was mounted in a receding contact angle meter (DSA-10,manufactured by KRUS), and water was charged on the substrate from aneedle to form 20 μL of a water droplet. After the needle was drawn outfrom the water droplet once, the needle was inserted into the waterdroplet again. Thus, the receding contact angle was measured at afrequency once per minute while aspirating the water droplet for 90seconds at a rate of 10 μL/min with this needle. Then, an average valueof the receding contact angle over 20 seconds after stable measurementswas given. Evaluation of the water repellency was made based on theaverage value as: being favorable “A” for no less than 70°, to; beingsomewhat favorable “B” for less than 70° and no less than 65°; and beinginferior “C” for less than 65°.

[Peel Resistance]

With respect to the substrate on which the organic film had beenlaminated, peeling of the organic film was also observed when thecontaminants on the surface of the substrate were determined afterremoving the immersion liquid in the evaluation of the contaminantremoving capability. Evaluation of the peel resistance was made based onthe results of this observation. In this test, when peeling of theorganic film was not observed, the peel resistance was evaluated to befavorable “A”; whereas when the peeling was observed, the peelresistance was evaluated to be inferior “B”.

TABLE 2 First heat treatment Second heat treatment Composition usedHeating Heating Contaminant in the cleaning temperature Heating timetemperature Heating time removing Water Peel method (° C.) (sec) (° C.)(sec) capability repellency resistance Example 1 Composition (1) 115 60180 60 A A A Example 2 Composition (2) 120 60 175 60 A A A Example 3Composition (3) 120 60 155 60 A A A Example 4 Composition (4) 100 60 18060 A A A Example 5 Composition (5) 115 60 170 60 A A A Example 6Composition (3) 115 60 180 60 A A A Example 7 Composition (5) 115 60 19060 A A A Example 8 Composition (1) 120 60 170 60 A A A Example 9Composition (2) 120 60 160 60 A A A Example 10 Composition (5) 120 60150 60 A A A Example 11 Composition (6) 120 60 120 60 A B A Example 12Composition (7) 130 60 190 60 A A A Example 13 Composition (8) 130 60190 60 A A A Example 14 Composition (9) 130 60 190 60 A A A Example 15Composition (10) 130 60 190 60 A A A Example 16 Composition (11) 130 60190 60 A A A Example 17 Composition (12) 130 60 190 60 A A A Example 18Composition (13) 130 60 190 60 A A A Comparative — — — — — B — — Example1

As is seen from the results shown in Table 2, Comparative Example inwhich the substrate does not have an organic film laminated thereonexhibited inferior contaminant removing capability, whereas all Examplesin which the substrate had an organic film was laminated thereonexhibited favorable contaminant removing capability.

According to the cleaning method of an immersion liquid, the compositionfor cleaning an immersion liquid and the substrate of the embodiment ofthe present invention, the immersion liquid containing contaminantsimmixed in the course of a formation process of a resist pattern carriedout using a liquid immersion lithography process can be readily andefficiently cleaned, thereby permitting reuse of the same. Therefore,the cleaning method of an immersion liquid of the embodiment of thepresent invention can be suitably applied to processes of manufacturingsemiconductor devices capable of forming finer resist patterns withsuperior resolving ability.

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

The invention claimed is:
 1. A cleaning method of an immersion liquid,comprising: supplying an immersion liquid on a surface of a cleaningsubstrate, the immersion liquid being to be used in a liquid immersionlithography apparatus, the cleaning substrate having a substrate and anorganic film laminated on a top face side of the substrate; and allowingthe immersion liquid to move on the cleaning substrate to removecontaminants from the immersion liquid, wherein the organic film is madefrom a composition comprising: a first polymer; a compound component;and a solvent, wherein the compound component consists of at least onecompound selected from the set consisting of a first compound having atleast two groups represented by formula (1), a second compound having agroup represented by formula (2) and a third compound having a grouprepresented by formula (3),

wherein, in the formula (1), R¹ represents a hydrogen atom or a methylgroup, and n is an integer of 0 to 10,

wherein, in the formula (2), each of R² and R³ independently representsa hydrogen atom or a group represented by formula (ii), and at leasteither one of R² and R³ represents a group represented by the formula(ii),

wherein, in the formula (ii), each of R⁴ and R⁵ independently representsa hydrogen atom, an alkyl group having 1 to 6 carbon atoms or analkoxyalkyl group having 1 to 6 carbon atoms, and, optionally, R⁴ and R⁵bind with each other to form a ring structure together with the carbonatom to which R⁴ and R⁵ each bind, and R⁶ represents a hydrogen atom oran alkyl group having 1 to 6 carbon atoms,

wherein, in the formula (3), each of R⁷ and R⁸ independently representsa single bond, a methylene group, an alkylene group having 2 to 20carbon atoms or a bivalent cyclic hydrocarbon group having 3 to 20carbon atoms, R⁹ represents an alkyl group having 1 to 20 carbon atomsor a monovalent cyclic hydrocarbon group having 3 to 20 carbon atoms,and m is 0 or
 1. 2. The cleaning method according to claim 1, whereinthe compound component consists of at least two compounds selected fromthe set consisting of the first compound, the second compound and thethird compound.
 3. The cleaning method according to claim 1, wherein thefirst polymer comprises a first structural unit represented by formula(4),

wherein, in the formula (4), R¹⁰ represents a hydrogen atom, a methylgroup or a trifluoromethyl group, and each of R¹¹, R¹² and R¹³independently represents an alkyl group having 1 to 20 carbon atoms or amonovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and,optionally, R¹¹ and R¹² bind with each other to form a ring structuretogether with the carbon atom to which R¹¹ and R¹² each bind, whereinall of hydrogen atoms of each of R¹¹, R¹² and R¹³ are unsubstituted orat least a part of hydrogen atoms of each of R¹¹, R¹² and R¹³ aresubstituted.
 4. The cleaning method according to claim 3, wherein thecomposition further comprises a second polymer comprising at least onefluorine atom.
 5. The cleaning method according to claim 4, wherein thesecond polymer comprises a structural unit represented by formula (5), astructural unit represented by formula (6) or a combination thereof,

wherein, in the formula (5), R¹⁴ represents a hydrogen atom, a methylgroup or a trifluoromethyl group, R¹⁵ represents a single bond, amethylene group, an alkylene group having 2 to 20 carbon atoms, abivalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, abivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or abivalent group combined thereof, wherein all of hydrogen atoms of R¹⁵are unsubstituted or at least a part of hydrogen atoms of R¹⁵ aresubstituted, R¹⁶ represents a fluorinated methylene group or afluorinate alkylene group having 2 to 20 carbon atoms, and R¹⁷represents a hydrogen atom or a monovalent organic group, wherein in theformula (6), R¹⁸ represents a hydrogen atom, a methyl group or atrifluoromethyl group, R¹⁹ represents a bivalent linking group, and R²⁰represents a fluorinated alkyl group having 1 to 20 carbon atoms or amonovalent fluorinated alicyclic hydrocarbon group having 3 to 20 carbonatoms.
 6. The cleaning method according to claim 1, wherein the firstcompound is represented by formula (1-1) or (1-2):

wherein, n¹ to n⁴ are each independently an integer of 0 to 10; R^(X1)to R^(X4) each independently represent a hydrogen atom or a grouprepresented by formula (i), and at least two of R^(X1) to R^(X4) are thegroup represented by the formula (i); n⁵ to n¹⁰ are each independentlyan integer of 0 to 10; R^(X5) to R^(X10) each independently represent ahydrogen atom or the group represented by the formula (i), and at leasttwo of R^(X5) to R^(X10) are the group represented by the followingformula (i):

wherein R¹ is as defined in formula (1).
 7. The cleaning methodaccording to claim 1, wherein the second compound is represented byformula (2-1):

wherein R² and R³ are each as defined in formula (2); and p is aninteger of 1 to
 3. 8. The cleaning method according to claim 1, whereinthe third compound is represented by formula (3-1):

wherein R⁸, R⁹ and m are each as defined in formula (3); and q is aninteger of 1 to
 3. 9. The cleaning method according to claim 1, whereinthe solvent comprises ketone, propylene glycol monoalkyl ether acetate,2-hydroxypropionic acid alkyl, 3-alkoxypropionic acid alkyl,γ-butyrolactone, or a mixture thereof.
 10. The cleaning method accordingto claim 1, wherein the composition further comprises an acid generator.11. The cleaning method according to claim 1, wherein the compositionfurther comprises an acid diffusion controlling agent.
 12. The cleaningmethod according to claim 1, wherein the composition further comprises asurfactant.